CN113861338B - Acrylamide terpolymer and preparation method and application thereof - Google Patents
Acrylamide terpolymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the research field of water plugging regulating materials and recovery efficiency improvement of oil fields, and discloses an acrylamide terpolymer and a preparation method and application thereof. The acrylamide terpolymer comprises a structural unit A, a structural unit B and a structural unit C; the structural unit A has a structure represented by formula (1); the structural unit B has a structure represented by formula (2); the structural unit C has a structure represented by formula (3); based on the total weight of the acrylamide terpolymer, the content of the structural unit A is 80-95wt%, the content of the structural unit B is 4-15wt%, and the content of the structural unit C is 1-5wt%;
Description
Technical Field
The invention relates to the research field of water plugging regulating materials and enhanced recovery ratio of oil fields, in particular to an acrylamide terpolymer and a preparation method and application thereof.
Background
The high-permeability oil reservoir in the victory oil field is in a development stage of high extraction degree (35.5%) and ultra-high water content (96.9%), the proportion of ineffective oil wells is increased day by day, and the operation cost per ton of oil is higher than 2500 yuan. How to change a large number of inefficient and ineffective wells into effective wells is an important issue facing the field. Meanwhile, a water layer and an oil layer in an oil reservoir stratum are mutually interwoven, the flooding is serious, the oil reservoir conditions are complex, the heterogeneity is serious, the two reservoirs are difficult to be effectively isolated by the existing construction technology, but in order to stabilize the yield of crude oil, a certain amount of water plugging materials are injected into an oil well, the oil-water ratio of produced liquid can be effectively adjusted, the productivity of the oil well is increased, and the method becomes a key technology for water injection development of the oil field. Indoor digital-analog and physical-analog researches also show that the saturation of the residual oil near the oil well is higher than that near the water well, the residual oil is easier to spread when the water is blocked in the oil well, and the characteristics of short, frequent and quick plugging can be realized. Although the existing water-based, oil-based, polymer gel and other water-blocking systems have certain selectivity, the water-blocking and oil-blocking systems have poor temperature resistance and salt resistance, so that the liquid volume of produced liquid is greatly reduced, and the popularization and application range is relatively small. Although the water-soluble polymer water shutoff agent can preferentially enter a stratum with higher water saturation, part of the water-soluble polymer water shutoff agent can enter an oil layer in stratum migration, and the water-soluble polymer water shutoff agent is very difficult to discharge because the water shutoff agent has no self-plugging removal capability. Although the oil-based cement water shutoff agent can also improve the crude oil recovery efficiency to a greater extent, the oil-based cement water shutoff agent has great disadvantages, for example, when the oil-based cement water shutoff agent flows into an oil-water mixed stratum, even if only a small part of stratum water is mixed in the oil layer, the oil-based cement water shutoff agent can react with the stratum water to solidify the cement, which indicates that the water shutoff selectivity of the oil-based cement water shutoff agent is greatly deficient. The polymer gel plugging agent enables the oil-water phase permeability to be reduced unevenly by means of the change of the effective movable volume under the action of oil and water, but the oil-water channel physical plugging can be caused by the treatment mode, so that the seepage capability of a porous medium is reduced, the oil production capability is also reduced while the water production of an oil well is greatly reduced, the liquid production capacity is too low due to improper treatment, and the production of crude oil is reduced.
In summary, most of the water plugging materials used for plugging water in the oil well at present are water-soluble polymers such as polyacrylamide and derivatives thereof, but due to poor selectivity, the oil phase permeability can be greatly reduced while plugging water, so that low liquid after plugging is caused, and the application of the water plugging technology of the oil well is restricted. Therefore, the novel acrylamide terpolymer is developed, the effects of water plugging and oil plugging prevention of complex oil reservoirs are realized, and the acrylamide terpolymer has important significance for improving the productivity of high-temperature oil reservoir oil wells. In addition, the development of the novel acrylamide terpolymer has important significance and wide application prospect for improving the storage capacity and the utilization rate of an oil-water transition zone, improving the oil yield of a high-water-content oil field and reducing the water yield of the high-water-content oil field.
Disclosure of Invention
The invention aims to overcome the problem of poor selectivity of a water plugging material of an oil well in the prior art, and provides an acrylamide terpolymer and a preparation method and application thereof, wherein the acrylamide terpolymer has excellent temperature resistance and salt resistance and plugging effect, and can realize the effect of controllable water plugging without oil plugging under the stratum conditions of high temperature (higher than 85 ℃) and high salt (the mineralization degree is 100,000mg/L).
In order to achieve the above object, a first aspect of the present invention provides an acrylamide terpolymer comprising a structural unit a, a structural unit B, and a structural unit C;
the structural unit A has a structure shown in a formula (1); the structural unit B has a structure shown in a formula (2); the structural unit C has a structure represented by formula (3); based on the total weight of the acrylamide terpolymer, the content of the structural unit A is 80-95wt%, the content of the structural unit B is 4-15wt%, and the content of the structural unit C is 1-5wt%;
wherein R is 1 、R 2 And R 5 Each independently is H or-CH 3 ，R 3 And R 4 Each independently is a C1-C4 alkyl group.
The second aspect of the present invention provides a method for preparing an acrylamide terpolymer, characterized in that the method comprises the steps of:
under the condition of solution polymerization reaction, in the presence of an initiator and a chain transfer agent, carrying out polymerization reaction on a monomer X, a monomer Y and a cross-linking agent M in water to obtain the acrylamide terpolymer; wherein the monomer X has a structure shown in a formula (4), the monomer Y has a structure shown in a formula (5), and the crosslinking agent M has a structure shown in a formula (6); based on the total weight of the monomer X, the monomer Y and the cross-linking agent M, the using amount of the monomer X is 80-95wt%, and the using amount of the monomer Y is 4-15wt%; the dosage of the cross-linking agent M is 1-5wt%;
wherein R is 1 ’、R 2 ' and R 5 ' each independently is H or-CH 3 ，R 3 ' and R 4 ' are each independently C1-C4 alkyl.
In a third aspect, the present invention provides an acrylamide terpolymer prepared by the above method.
The invention also provides the application of the acrylamide terpolymer as a water plugging material.
By the technical scheme, the acrylamide terpolymer and the preparation method and application thereof have the following beneficial effects:
the invention introduces a functional monomer and an oil-soluble cross-linking agent into an acrylamide polymer macromolecular chain, initiates polymerization to obtain polymer colloid, and obtains the acrylamide terpolymer after granulation and drying. The introduction of the functional monomer can greatly improve the temperature resistance and salt resistance of the polymer, the introduction of the oil-soluble cross-linking agent can obtain a weak gel system in the polymerization process, and the weak gel system can continuously generate cross-linking reaction in the water phase of a high-temperature oil reservoir to form a strong gel system, so that the plugging strength of the water phase of the oil reservoir is greatly improved. That is to say, after the acrylamide terpolymer is injected into an oil reservoir stratum, the acrylamide terpolymer can preferentially enter a water phase layer, and under the synergistic action of high temperature (more than 85 ℃) of an oil reservoir and a chain transfer agent, a cross-linking agent can further generate a cross-linking effect to form a three-dimensional network structure, so that super gel is obtained, the water phase permeability is effectively reduced, and the water phase plugging effect is enhanced; after the acrylamide terpolymer meets the oil phase, the oil-soluble cross-linking agent can be released and dissolved in the crude oil, so that the formation of gel and the influence on the oil phase permeability are avoided. Therefore, the effect of controllable water plugging and oil plugging of the oil reservoir can be realized, measures are provided for creating and increasing the efficiency of ineffective and low-efficiency wells, and technical support is provided for improving the productivity of the oil well in the ultra-high water-cut period.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides an acrylamide terpolymer characterized by comprising a structural unit a, a structural unit B, and a structural unit C;
the structural unit A has a structure shown in a formula (1); the structural unit B has a structure represented by formula (2); the structural unit C has a structure represented by formula (3); based on the total weight of the acrylamide terpolymer, the content of the structural unit A is 80-95wt%, the content of the structural unit B is 4-15wt%, and the content of the structural unit C is 1-5wt%;
wherein R is 1 、R 2 And R 5 Each independently is H or-CH 3 ，R 3 And R 4 Each independently is a C1-C4 alkyl group.
In the invention, the oil-soluble structural unit B and the structural unit C with a crosslinking function are introduced into the molecular chain of the polyacrylamide, so that the temperature resistance and salt resistance of the prepared acrylamide terpolymer can be obviously improved; furthermore, due to the introduction of the structural unit C, polyacrylamide is in a weak gel system in the polymerization process, and a strong gel system is formed in a high-temperature oil reservoir water phase, so that the oil reservoir water phase plugging strength can be remarkably improved.
Further, based on the total weight of the acrylamide terpolymer, the content of the structural unit A is 85-90wt%, the content of the structural unit B is 5-10wt%, and the content of the structural unit C is 2-4wt%.
In the present invention, the total content of the structural unit A, the structural unit B and the structural unit C is 100wt%.
In the present invention, the content of each structural unit in the copolymer can be measured by a conventional method in the prior art, such as infrared spectroscopy, nuclear magnetism, and the amount of monomer charged during polymerization.
In the invention, the content of each structural unit in the polymer is determined by adopting the monomer feeding amount, and specifically, the feeding ratio of each monomer actually participating in polymerization is determined by testing the content of the unreacted monomer, so that the content of each structural unit in the polymer is determined.
Further, in the present invention, when the content of each unreacted monomer in the tested polymer is 0.02 wt% or less, it is indicated that substantially all the monomers participate in the polymerization reaction. Specifically, the content of the residual monomer is measured by liquid chromatography.
According to the invention, preferably R 1 、R 2 And R 5 Is H, R 3 And R 4 Is C1-C2 alkyl.
According to the invention, under the conditions of high temperature (more than 85 ℃) and high salt (the mineralization degree is 100,000mg/L), the apparent viscosity of the controllable water plugging material is more than 30mPa & s, and preferably 40-60mPa & s.
In the invention, the apparent viscosity of the acrylamide terpolymer is measured by adopting a Brookfield viscometer, and particularly, the apparent viscosity of a water-blocking material (the mass concentration is 2000 mg/L) is measured at a specified test temperature and mineralization degree.
The second aspect of the present invention provides a method for preparing an acrylamide terpolymer, characterized in that the method comprises the steps of:
under the condition of solution polymerization reaction, in the presence of an initiator and a chain transfer agent, carrying out polymerization reaction on a monomer X, a monomer Y and a cross-linking agent M in water to obtain the acrylamide terpolymer; wherein the monomer X has a structure shown in a formula (4), the monomer Y has a structure shown in a formula (5), and the crosslinking agent M has a structure shown in a formula (6); based on the total weight of the monomer X, the monomer Y and the cross-linking agent M, the using amount of the monomer X is 80-95wt%, and the using amount of the monomer Y is 4-15wt%; the dosage of the cross-linking agent M is 1-5wt%;
wherein R is 1 ’、R 2 ' and R 5 ' each independently is H or-CH 3 ，R 3 ' and R 4 ' are each independently C1-C4 alkyl.
According to the invention, the monomer X with the structure shown in the formula (4), the monomer Y with the structure shown in the formula (5) and the cross-linking agent M with the structure shown in the formula (6) are copolymerized to obtain the acrylamide terpolymer, and the obtained acrylamide terpolymer has excellent salt resistance and salt tolerance, can be further cross-linked under the condition of a high-temperature oil reservoir (more than 85 ℃) to form a three-dimensional network structure, forms super-strong gel, effectively reduces the water phase permeability, and increases the water phase blocking effect; after the acrylamide terpolymer meets an oil phase, the oil-soluble cross-linking agent can be released and dissolved in crude oil, so that the formation of gel and the influence on the oil phase permeability are avoided, and the selective water plugging effect is realized.
In the invention, in the polymerization process of the cross-linking agent M with the monomer X and the monomer Y, under the polymerization temperature condition of the invention, the carbonyl group exists in the formula (6), so that the polymerization activity of the carbonyl group ortho-position double bond is higher than that of the double bond at the allyl group, and the double bond mainly in the carbonyl group ortho-position in the cross-linking agent M can generate copolymerization reaction with the monomer X and the monomer Y. When the acrylamide terpolymer is tested by nuclear magnetism, the existence of carbon-carbon double bonds in the copolymer can be confirmed, and the fact that all the double bonds of the crosslinking agent M do not participate in the reaction is confirmed.
According to the invention, based on the total weight of the monomer X, the monomer Y and the cross-linking agent M, the dosage of the monomer X is 85-90wt%, and the dosage of the monomer Y is 5-10wt%; the amount of the cross-linking agent M is 2-4wt%.
In a preferred embodiment of the present invention, the monomer X represented by the formula (4) is acrylamide (R) 1 ' is H) or methacrylamide (R) 1 ' is CH 3 ) (ii) a The monomer Y shown as the formula (5) is 2-acrylamide-2-methoxy methyl acetate (R) 2 ' is H, R 3 ' and R 4 ' is CH 3 ) Or 2-acrylamido-2-ethoxyacetic acid ethyl ester (R) 2 ' is H, R 3 ' and R 4 ' is CH 2 CH 3 ) (ii) a The crosslinking agent M shown as the formula (6) is N, N-diallyl acrylamide (R) 5 ' is H) or N, N-diallylmethylacrylamide (R) 5 ' is CH 3 )。
In the present invention, the monomer X, the monomer Y and the crosslinking agent M are all commercially available.
In the present invention, the amount of water used is such that the total mass concentration of the monomer X, the monomer Y and the crosslinking agent M in the solution polymerization reaction system is 10 to 30% by weight.
According to the present invention, the conditions of the solution polymerization reaction include: the initiator is an oxidation-reduction system initiator, and the chain transfer agent is 2,5-dithiobiurea; the reaction temperature is 30-60 ℃, and the reaction time is 6-8h.
According to the present invention, the solution polymerization conditions further comprise: in the presence of an emulsifier.
In the invention, the emulsifier can emulsify the monomer X, the monomer Y and the cross-linking agent M to form stable emulsion, and the existence of the cross-linking agent enables the acrylamide terpolymer to be further cross-linked at high temperature (more than 85 ℃) of an oil reservoir, so that a weak gel system is changed into super-strong gel, the water phase permeability is effectively reduced, and the water phase plugging effect is enhanced.
According to the invention, the amount of the initiator is 0.15-0.75wt% based on the total weight of the monomer X, the monomer Y and the cross-linking agent M; the amount of the chain transfer agent is 0.5-2wt%; the amount of the emulsifier is 1-5wt%.
In the present invention, the oxidation-reduction system initiator may be a conventional oxidation-reduction system initiator in the art, and is preferably a persulfate oxidizer and a sulfite reducer.
Specifically, the persulfate oxidizer may be, for example, potassium persulfate, ammonium persulfate, or the like. The sulfite reducing agent may be, for example, potassium bisulfite, sodium bisulfite or the like.
Specifically, the use amount of the persulfate oxidizer is 0.1-0.5wt% based on the total weight of the monomer X, the monomer Y and the crosslinking agent M; the amount of the sulfite reducing agent is 0.05 to 0.25wt%.
According to the invention, the emulsifier is selected from at least one of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60 and tween 80.
In the present invention, it is preferable to granulate and dry the acrylamide terpolymer obtained by polymerization.
In a preferred embodiment of the present invention, the method for preparing the acrylamide terpolymer comprises:
step 1, weighing a monomer X to prepare an aqueous solution;
step 2, weighing a monomer Y, a cross-linking agent M and an emulsifying agent, adding the monomer Y, the cross-linking agent M and the emulsifying agent into the solution, and uniformly stirring to form a stable micelle;
the emulsifier is at least one of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60 and tween 80;
and 3, adding a chain transfer agent and an initiator into the micelle solution obtained in the step 2, uniformly stirring, raising the temperature to 30-60 ℃, initiating polymerization for 6-8 hours to obtain polymer colloid, and granulating and drying to obtain the acrylamide terpolymer.
In a third aspect, the present invention provides an acrylamide terpolymer prepared by the above method.
The invention provides the application of the acrylamide terpolymer as a water plugging material in a fourth aspect.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
a monomer X represented by the formula (4) (in X1, R) 1 ' is H; in X2, R 1 ' is CH 3 ) And a monomer Y represented by the formula (5) (in Y1, R 2 ' is H, R 3 ' and R 4 ' is CH 3 (ii) a In Y2, R 2 ' is H, R 3 ' and R 4 ' is CH 2 CH 3 ) And a crosslinking agent M represented by the formula (6) (in M1, R 5 ' is H; in M2, R 5 ' is CH 3 ) Purchased from Shanghai Aladdin Biotechnology, inc.;
examples and comparative examples all other raw materials were commercially available;
in the following examples, the apparent viscosity of acrylamide terpolymers was measured using a Brookfield viscometer, specifically, the apparent viscosity of water-blocking materials (2000 mg/L by mass) at the specified test temperature and degree of mineralization.
The plugging rate is measured on a rock core flow test device according to the plugging rate test procedure in SY/T5840-2007 in the indoor test method of bridging plugging materials for drilling fluid. Specifically, the method comprises the following steps:
and (3) measuring the water plugging rate: loading the artificial core into core holder, saturating with water, and measuring its pore volume PV and water phase permeability (K) w1 ) Then injecting 1.0PV water plugging material, curing at high temperature for 24h, and measuring the permeability (K) of the mixture after adding the water plugging agent by using water w2 )，1-(K w2 /K w1 ) And multiplying 100 percent to obtain the water plugging rate.
And (3) measuring the oil plugging rate: loading the artificial core into core holder, saturating with oil, and measuring its pore volume PV and oil phase permeability (K) o1 ) Then injecting 1.0PV water plugging material, curing at high temperature for 24h, and measuring the permeability (K) of the mixture after adding the water plugging agent by using oil o2 )，1-(K o2 /K o1 ) X 100% is the oil plugging rate。
Wherein the artificial core is obtained by filling quartz sand of 40-60 meshes in a mould.
Example 1
1. Weighing 38g of acrylamide (monomer X1) and adding the acrylamide into a polymerization kettle filled with 200mL of water, and fully stirring and dissolving to obtain a stable aqueous solution;
2. weighing 1.6g of 2-acrylamide-2-methoxy methyl acetate (monomer Y1), 0.4g of oil-soluble cross-linking agent (cross-linking agent M1) and 2g of emulsifier span 40, adding into the solution, and fully stirring to form stable micelles;
3. and (3) adding 0.6g of chain transfer agent into the micelle in the step 2, sequentially adding 0.15g of potassium persulfate and 0.075g of sodium bisulfite, fully stirring to ensure that the mixture enters the micelle, raising the temperature to 40 ℃ to initiate polymerization for 7 hours to obtain colloid, and granulating and drying to obtain the acrylamide terpolymer X1.
According to the calculation of the material charging amount and the raw material allowance, based on the total weight of the acrylamide terpolymer X1, the content of the structural unit provided by the monomer X is 95 weight percent, the content of the structural unit provided by the monomer Y is 4 weight percent, and the content of the structural unit C provided by the crosslinking agent M is 1 weight percent.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 100,000mg/L), the apparent viscosity of the acrylamide terpolymer is 50.4 mPas, delamination does not occur for more than 30 days, and the water blocking rate and the oil blocking rate of the acrylamide terpolymer X1 are respectively 99.7% and 7.2%.
Example 2
1. Weighing 32g of acrylamide (monomer X1) and adding the acrylamide into a polymerization kettle filled with 200mL of water, and fully stirring and dissolving to obtain a stable aqueous solution;
2. 6g of 2-acrylamide-2-methoxy methyl acetate (monomer Y1), 2.0g of oil-soluble cross-linking agent (cross-linking agent M1) and 1.9g of emulsifier span 80 are weighed and added into the solution, and stable micelles are formed after full stirring;
3. and (3) adding 0.8g of chain transfer agent into the micelle in the step (2), then sequentially adding 0.2g of potassium persulfate and 0.1g of sodium bisulfite, fully stirring to ensure that the mixture enters the micelle, raising the temperature to 45 ℃ to initiate polymerization for 7 hours to obtain colloid, and granulating and drying to obtain the acrylamide terpolymer X2.
According to the calculation of the material charging amount and the raw material allowance, based on the total weight of the acrylamide terpolymer X2, the content of the structural unit provided by the monomer X is 80 wt%, the content of the structural unit provided by the monomer Y is 15wt%, and the content of the structural unit C provided by the crosslinking agent M is 5wt%.
Tests show that under the conditions of high temperature (100 ℃) and high salt (the mineralization is 100,000mg/L), the apparent viscosity of the acrylamide terpolymer is 48.6 mPas, the delamination does not occur for more than 30 days, and the water blocking rate and the oil blocking rate of the acrylamide terpolymer X2 are respectively 99.1% and 10.9%.
Example 3
1. Weighing 36g of acrylamide (monomer X1) and adding the acrylamide into a polymerization kettle filled with 200mL of water, and fully stirring and dissolving to obtain a stable aqueous solution;
2. weighing 2.8g of 2-acrylamide-2-methoxy methyl acetate (monomer Y1), 1.2g of oil-soluble cross-linking agent (cross-linking agent M1) and 1.4g of emulsifier Tween 60, adding into the above solution, and fully stirring to form stable micelle;
3. and (3) adding 0.45g of chain transfer agent into the micelle in the step 2, sequentially adding 0.05g of potassium persulfate and 0.025g of sodium bisulfite, fully stirring to ensure that the mixture enters the micelle, raising the temperature to 60 ℃ to initiate polymerization for 7 hours to obtain colloid, and granulating and drying to obtain the acrylamide terpolymer X3.
According to the calculation of the material charging amount and the raw material allowance, based on the total weight of the acrylamide terpolymer X3, the content of the structural unit provided by the monomer X is 90wt%, the content of the structural unit provided by the monomer Y is 7 wt%, and the content of the structural unit C provided by the crosslinking agent M is 3 wt%.
Tests show that under the conditions of high temperature (115 ℃) and high salt (the mineralization degree is 100,000mg/L), the apparent viscosity of the acrylamide terpolymer is 54.9mPa & s, no delamination occurs after more than 30 days, and the water blocking rate and the oil blocking rate of the acrylamide terpolymer X3 are respectively 99.9% and 4.4%.
Example 4
1. Weighing 35.5g of acrylamide (monomer X1) and adding the acrylamide into a polymerization kettle filled with 200mL of water, and fully stirring and dissolving to obtain a stable aqueous solution;
2. 3.6g of 2-acrylamide-2-methoxy methyl acetate (monomer Y1), 0.9g of oil-soluble cross-linking agent (cross-linking agent M1) and 1.8g of emulsifier Tween 80 are weighed and added into the solution, and stable micelles are formed after full stirring;
3. and (3) adding 0.3g of chain transfer agent into the micelle in the step (2), then sequentially adding 0.05g of potassium persulfate and 0.025g of sodium bisulfite, fully stirring to ensure that the mixture enters the micelle, raising the temperature to 55 ℃ to initiate polymerization for 7 hours to obtain colloid, and granulating and drying to obtain the acrylamide terpolymer X4.
According to the calculation of the material charging amount and the raw material balance, based on the total weight of the acrylamide terpolymer X4, the content of the structural unit provided by the monomer X is 88.75 wt%, the content of the structural unit provided by the monomer Y is 9 wt%, and the content of the structural unit C provided by the crosslinking agent M is 2.25 wt%.
Tests show that under the conditions of high temperature (115 ℃) and high salt (the mineralization degree is 100,000mg/L), the apparent viscosity of the acrylamide terpolymer is 56.7mPa & s, no delamination occurs after more than 30 days, and the water blocking rate and the oil blocking rate of the acrylamide terpolymer X4 are 99.5% and 4.2%, respectively.
Example 5
An acrylamide terpolymer was prepared as in example 1, except that: monomer X1 was replaced by methacrylamide (monomer X2).
According to the test, under the conditions of high temperature (90 ℃) and high salt (the degree of mineralization is 100,000mg/L), the apparent viscosity of the acrylamide terpolymer is 43.9mPa & s, the acrylamide terpolymer does not delaminate after exceeding 30 days, and the water plugging rate and the oil plugging rate of the acrylamide terpolymer X5 are respectively 96.7% and 8.4%.
Example 6
An acrylamide terpolymer was prepared as in example 1, except that: 2-acrylamido-2-methoxy ethyl acetate (monomer Y2) was used in place of monomer Y1.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 100,000mg/L), the apparent viscosity of the acrylamide terpolymer is 45.3mPa & s, no delamination occurs after more than 30 days, and the water blocking rate and the oil blocking rate of the acrylamide terpolymer X6 are 93.4% and 9.6%, respectively.
Example 7
An acrylamide terpolymer was prepared as in example 1, except that: the crosslinking agent M1 is replaced by a crosslinking agent M2.
According to the test, under the conditions of high temperature (90 ℃) and high salt (the degree of mineralization is 100,000mg/L), the apparent viscosity of the acrylamide terpolymer is 40.4mPa & s, the acrylamide terpolymer does not delaminate after exceeding 30 days, and the water plugging rate and the oil plugging rate of the acrylamide terpolymer X7 are respectively 92.8% and 9.5%.
Comparative example 1
An acrylamide terpolymer was prepared as in example 1, except that: no crosslinker M was added. To obtain the acrylamide terpolymer D1.
According to the calculation of the charging amount, the content of the structural unit provided by the monomer X is 96 weight percent and the content of the structural unit provided by the monomer Y is 4 weight percent based on the total weight of the acrylamide terpolymer D1.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 100,000mg/L), the apparent viscosity of the acrylamide terpolymer is 22.3mPa & s, obvious delamination occurs after 3 days, and the water plugging rate and the oil plugging rate of the acrylamide terpolymer D1 are 70.5% and 11.6%, respectively.
Comparative example 2
An acrylamide terpolymer was prepared according to the method of example 1, except that: monomer Y1 was not added. To obtain the acrylamide terpolymer D2.
The amount of the structural unit C provided by the monomer X and the crosslinking agent M was determined to be 98.9 wt% and 1.1 wt% based on the total weight of the acrylamide terpolymer D2.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 100,000mg/L), the apparent viscosity of the acrylamide terpolymer is 26.4 mPas, obvious delamination occurs after 5 days, and the water plugging rate of the acrylamide terpolymer D2 is 75.8 percent, and the oil plugging rate is 40.2 percent.
Comparative example 3
An acrylamide terpolymer D3 was prepared as in example 1, except that: the amounts of monomer X1, monomer Y1 and crosslinking agent M1 used were different from those of example 1. Based on the total weight of the acrylamide terpolymer, the content of the structural unit provided by the monomer X is 65 wt%, the content of the structural unit provided by the monomer Y is 20 wt%, and the content of the structural unit C provided by the crosslinking agent M is 15 wt%.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization degree is 100,000mg/L), the apparent viscosity of the acrylamide terpolymer D3 is 28.9mPa & s, obvious layering occurs after 6 days, and the water plugging rate of the acrylamide terpolymer D3 as a water plugging material is 72.8 percent, and the oil plugging rate is 15.4 percent.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. An acrylamide terpolymer characterized by comprising a structural unit A, a structural unit B and a structural unit C;
the structural unit A has a structure shown in a formula (1); the structural unit B has a structure represented by formula (2); the structural unit C has a structure represented by formula (3); based on the total weight of the acrylamide terpolymer, the content of the structural unit A is 80-95wt%, the content of the structural unit B is 4-15wt%, and the content of the structural unit C is 1-5wt%;
wherein R is 1 、R 2 And R 5 Each independently is H or-CH 3 ，R 3 And R 4 Each independently is a C1-C4 alkyl group.
2. The acrylamide terpolymer according to claim 1 wherein the amount of structural unit a is 85-90wt%, the amount of structural unit B is 5-10wt%, and the amount of structural unit C is 2-4wt%, based on the total weight of the acrylamide terpolymer.
3. The acrylamide terpolymer according to claim 1 or 2, wherein R 1 、R 2 And R 5 Is H, R 3 And R 4 Is C1-C2 alkyl.
4. A method of making an acrylamide terpolymer, comprising the steps of:
under the condition of solution polymerization reaction, in the presence of an initiator and a chain transfer agent, carrying out polymerization reaction on a monomer X, a monomer Y and a cross-linking agent M in water to obtain the acrylamide terpolymer; wherein the monomer X has a structure shown in a formula (4), the monomer Y has a structure shown in a formula (5), and the crosslinking agent M has a structure shown in a formula (6); based on the total weight of the monomer X, the monomer Y and the cross-linking agent M, the using amount of the monomer X is 80-95wt%, and the using amount of the monomer Y is 4-15wt%; the dosage of the cross-linking agent M is 1-5wt%;
wherein R is 1 ’、R 2 ' and R 5 ' each independently is H or-CH 3 ，R 3 ' and R 4 ' are each independently C1-C4 alkyl.
5. The method of claim 4, wherein monomer X is present in an amount of 85 to 90wt% and monomer Y is present in an amount of 5 to 10wt%, based on the total weight of monomer X, monomer Y, and crosslinker M; the amount of the cross-linking agent M is 2-4wt%.
6. The method of claim 4 or 5, wherein the conditions of the solution polymerization reaction comprise: the initiator is an oxidation-reduction system initiator, and the chain transfer agent is 2,5-dithiobiurea; the reaction temperature is 30-60 ℃, and the reaction time is 6-8h.
7. The method of claim 4 or 5, wherein the solution polymerization conditions further comprise: in the presence of an emulsifier.
8. The process of claim 7 wherein the initiator is present in an amount of from 0.15 to 0.75 weight percent, based on the total weight of monomer X, monomer Y and crosslinker M; the dosage of the chain transfer agent is 0.5-2wt%; the amount of the emulsifier is 1-5wt%.
9. The method according to claim 6, wherein the oxidation-reduction system initiator is a persulfate oxidizer and a sulfite reducer.
10. The method of claim 7, wherein the emulsifier is selected from at least one of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60 and tween 80.
11. An acrylamide terpolymer obtainable by the process according to any one of claims 4-10.
12. Use of the acrylamide terpolymer according to any one of claims 1-3 and 11 as a water shutoff material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6171386B1 (en) * | 1998-01-22 | 2001-01-09 | Benchmark Research& Technology Inc. | Cementing compositions, a method of making therefor, and a method for cementing wells |
| US6306203B1 (en) * | 1999-09-23 | 2001-10-23 | Xerox Corporation | Phase change inks |
| CN1730502A (en) * | 2005-08-16 | 2006-02-08 | 广东鸿昌化工有限公司 | Microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature and its production method |
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| US8871882B2 (en) * | 2012-02-14 | 2014-10-28 | Akron Polymer Systems, Inc. | Method for the preparation of styrenic fluoropolymers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6171386B1 (en) * | 1998-01-22 | 2001-01-09 | Benchmark Research& Technology Inc. | Cementing compositions, a method of making therefor, and a method for cementing wells |
| US6306203B1 (en) * | 1999-09-23 | 2001-10-23 | Xerox Corporation | Phase change inks |
| CN1730502A (en) * | 2005-08-16 | 2006-02-08 | 广东鸿昌化工有限公司 | Microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature and its production method |
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